Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The c...Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The complexes have the absorption and emission maximum in the range 452 - 468 nm and 594 - 617 nm respectively. The static nature of quenching is confirmed from the ground state absorption studies. The association constants for the complexes with quinones are calculated from the Benesi-Hildebrand plots using absorption spectral data. The value of quenching rate constant (kq) is highly sensitive to the nature of the ligand and the quencher, the medium, structure and size of the quenchers. Compared to the aqueous medium, the electron transfer rate is altered in CTAB medium. The oxidative nature of the quenching is confirmed by the formation of Ru3+ ion and quinone anion radical.展开更多
The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru（II） complexes [Ru（terpy）（phen）X]＋ （terpy=2,2＇,6＇,2″-terpyridine...The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru（II） complexes [Ru（terpy）（phen）X]＋ （terpy=2,2＇,6＇,2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH （1）, X=Cl （2）, X-CN （3）） were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π＊（terpy） type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz （Ru）＋Tr/p（X）--π＊ （terpy） transition with MLCT/XLCT （metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer） character, whereas that of 3 at 529 nm is related to a dyz （Ru）＋π（terpy）-π＊ （terpy） transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm （1）, 913 nm （2）, and 838 nm （3） have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru（II） complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.展开更多
Structure Activity-Relationships (SARs) of the five possible isomers of RuCl<sub>2</sub>(Azpy)<sub>2</sub> were predicted thanks to DFT method. Azpy stands for 2-phenylazopyridine and the struc...Structure Activity-Relationships (SARs) of the five possible isomers of RuCl<sub>2</sub>(Azpy)<sub>2</sub> were predicted thanks to DFT method. Azpy stands for 2-phenylazopyridine and the structure of the isomers α-RuCl<sub>2</sub>(Azpy)<sub>2</sub>, β-RuCl<sub>2</sub>(Azpy)<sub>2</sub>, γ-RuCl2(Azpy)2, δ-RuCl<sub>2</sub>(Azpy)<sub>2</sub> and ε-RuCl<sub>2</sub>(Azpy)<sub>2</sub> call respectively α-Cl, β-Cl, γ-Cl, δ-Cl and ε-Cl are defined according to chlorine atoms orientations. Hence, they are divided into two groups. In the first group comprising α-Cl, β-Cl and ε-Cl, both chlorine atoms are in cis position and Azpy ligands are intervertical. Whereas the two others isomers (γ-Cl and δ-Cl), they form the second group. Here, both chlorine are in trans position and Azpy are planar. The five synthesized isomers were investigated as potential antitumor agents. Then, regarding the DNA, its bases are stacked by pair. Therefore, complexes are assumed to insert and to stack on them through intercalative mode. So the electronic and geometric structures become more important to describe their SARs. Consequently, group 2 regarding γ-Cl and δ-Cl presents the best structure to allow intercalation between DNA base-pairs. Besides, the energy order of the lower unoccupied molecular orbital (LUMO) of the isomers is ELUMO(β-Cl) > ELUMO(α-Cl) > ELUMO(ε-Cl) > ELUMO(γ-Cl) > ELUMO(δ-Cl). The energy gap between LUMO and HOMO was also sorted as Δ(L-H)(β-Cl) > Δ(L-H)(α-Cl) > Δ(L-H)(ε-Cl) > Δ(L-H)(γ-Cl) > Δ(L-H)(δ-Cl). In addition, the total dipole moment was classified as μ(ε-Cl) > μ(β-Cl) > μ(α-Cl) > μ(γ-Cl) > μ(δ-Cl). Finally, net charge of the ligand Azpy was also classified as QL(δ-Cl) > QL(γ-Cl) > QL(ε-Cl) > QL(α-Cl) > QL(β-Cl). All those parameters show that δ-Cl isomer displays the highest activity as antitumor drug when intercalating between the DNA basepairs Cytosine-Guanine/Cytosine-Guanine (CG/CG).展开更多
The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order...The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.展开更多
In view of the growing interest for the synthesis of metal complexes and their interaction with DNA, we have synthesized and characterized two complexes containing ruthenium as metal center. The complexes are of the t...In view of the growing interest for the synthesis of metal complexes and their interaction with DNA, we have synthesized and characterized two complexes containing ruthenium as metal center. The complexes are of the type [Ru（dppz）L4]（C104）2 where L are biologically important ligands such as pyrazole and dimethylpyrazole. The characterization of these complexes is done by 1 H NMR, 13C NMR, elemental analysis and mass spectroscopy. The interaction of these complexes with CT DNA was monitored and binding constants were determined using absorption and fluorescence spectroscopy. The mode of binding was found to be intercalative for both complexes and was determined using hydrodynamic viscosity studies. The complexes were further studied for photocleavage studies with supercoiled plasmid pBR322 DNA.展开更多
A biomolecule-free photoelectrochemical(PEC) probe(denoted as Ru-1) was designed, synthesized and coupled with TiO2 nanoparticles(NPs) for the highly sensitive and selective PEC detection of Hg^2+, a model analyte wit...A biomolecule-free photoelectrochemical(PEC) probe(denoted as Ru-1) was designed, synthesized and coupled with TiO2 nanoparticles(NPs) for the highly sensitive and selective PEC detection of Hg^2+, a model analyte with hypertoxicity to both human health and ecosystem. The probe Ru-1 was designed with Ru(Ⅱ) bipyridyl complex as the chromophore, thiocyanate ligand as the recognition unit, and carboxylate group as the linkage site to connect Ru-1 to TiO2 nanoparticles. Under irradiation, Ru-1 shows strong affinity to TiO2 and good photophysical properties of strong visible light absorption, slow electron-hole(e-h^+) recombination, and fast photoelectron injection to TiO2 nanoparticles via the bridge of 4-(2,2-bipyridin)-4-yl-thiophene moiety. However, the specific coordination of Hg^2+ with Ru-1 via the thiol moiety in the thiocyanate enlarges the band gap of tlie complex and reduces the photocurrent significantly. The synergistic interaction between TiO2 nanoparticles and the Ru-1 complex led to a selective PEC sensing strategy for Hg^2+ detection. Detectable linear ranges from 10^-12 g/mL to 10^-7 g/mL and from 10^-7g/mL to 10^-3 g/mL were obtained without the interference from possibly co-existed metal ions. The good analytical performances indicate the chemical probe based biomolecule-free PEC platform may offer a new route for the detection of biologically and environmentally important small molecules.展开更多
Ground state geometries, natural bond orbital (NBO), analysis of frontier molecular orbitals (FMOs), analysis and spectral (RMN and UV-Visible) properties of five azopyridine ruthenium (II) complexes α-Cl, β-Cl, γ-...Ground state geometries, natural bond orbital (NBO), analysis of frontier molecular orbitals (FMOs), analysis and spectral (RMN and UV-Visible) properties of five azopyridine ruthenium (II) complexes α-Cl, β-Cl, γ-Cl, δ-Cl and ε-Cl of RuCl2(Dazpy)2 have been theoretically studied by the Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods using two basis sets: Lanl2DZ and a generic basis set in gas or in chloroform solvent. Dazpy stands for 4,6-dimethyl-phenylazopyridine. Optimized geometry shows that, except β-Cl, all the other four isomers α-Cl, γ-Cl, δ-Cl and ε-Cl are C2 symmetrical. Otherwise, a good agreement was found between experimental and the calculated geometry and NMR data. Moreover, Lanl2DZ effective core potential basis set provides good chemical shifts and geometric properties. Furthermore, the prediction of the frontier orbitals (Highest Occupied Molecular Orbital or HOMO and Lowest Unoc-cupied Molecular Orbital or LUMO) shows that the most active isomer suita-ble for electronic reactions is admitted to be δ-Cl. Besides, the NBO analysis indicates that the Ru-N is formed by the electron delocalization of lone pair atomic orbital of N2 and Npy to Ru. Also, the strongest interactions between LP(N) with LP*(Ru) and LP(Cl) with LP*(Ru) stabilize the molecular struc-ture. In addition, NBO shows that the five d orbitals of Ru in the complex are organized so that there is no order of priority from one complex to another. Therefore, the transition LP(Ru) → π*(N1 = N2) corresponding to Metal to Li-gand Charge Transfer (MLCT) is in reality no more than d → π*. Besides, TDDFT prediction in chloroform solvent reveals that all the five isomerics complexes absorb in the visible region as well as efficient photosensitizers. What’s more, δ-RuCl2(dazpy)2 can potentially act as the excellent sensitizer with a large band of absorption in visible region and a small excited energy. This study can help design and find out the ability or properties of the com-plex to behave as sensitizer or potential cancer drugs.展开更多
文摘Photoinduced electron transfer reaction between the excited state ruthenium (II) polypyridyl complexes and quinones has been investigated in cetyltrimethylammonium bromide using luminescent quenching techniques. The complexes have the absorption and emission maximum in the range 452 - 468 nm and 594 - 617 nm respectively. The static nature of quenching is confirmed from the ground state absorption studies. The association constants for the complexes with quinones are calculated from the Benesi-Hildebrand plots using absorption spectral data. The value of quenching rate constant (kq) is highly sensitive to the nature of the ligand and the quencher, the medium, structure and size of the quenchers. Compared to the aqueous medium, the electron transfer rate is altered in CTAB medium. The oxidative nature of the quenching is confirmed by the formation of Ru3+ ion and quinone anion radical.
文摘The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru（II） complexes [Ru（terpy）（phen）X]＋ （terpy=2,2＇,6＇,2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH （1）, X=Cl （2）, X-CN （3）） were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π＊（terpy） type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz （Ru）＋Tr/p（X）--π＊ （terpy） transition with MLCT/XLCT （metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer） character, whereas that of 3 at 529 nm is related to a dyz （Ru）＋π（terpy）-π＊ （terpy） transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm （1）, 913 nm （2）, and 838 nm （3） have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru（II） complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.
文摘Structure Activity-Relationships (SARs) of the five possible isomers of RuCl<sub>2</sub>(Azpy)<sub>2</sub> were predicted thanks to DFT method. Azpy stands for 2-phenylazopyridine and the structure of the isomers α-RuCl<sub>2</sub>(Azpy)<sub>2</sub>, β-RuCl<sub>2</sub>(Azpy)<sub>2</sub>, γ-RuCl2(Azpy)2, δ-RuCl<sub>2</sub>(Azpy)<sub>2</sub> and ε-RuCl<sub>2</sub>(Azpy)<sub>2</sub> call respectively α-Cl, β-Cl, γ-Cl, δ-Cl and ε-Cl are defined according to chlorine atoms orientations. Hence, they are divided into two groups. In the first group comprising α-Cl, β-Cl and ε-Cl, both chlorine atoms are in cis position and Azpy ligands are intervertical. Whereas the two others isomers (γ-Cl and δ-Cl), they form the second group. Here, both chlorine are in trans position and Azpy are planar. The five synthesized isomers were investigated as potential antitumor agents. Then, regarding the DNA, its bases are stacked by pair. Therefore, complexes are assumed to insert and to stack on them through intercalative mode. So the electronic and geometric structures become more important to describe their SARs. Consequently, group 2 regarding γ-Cl and δ-Cl presents the best structure to allow intercalation between DNA base-pairs. Besides, the energy order of the lower unoccupied molecular orbital (LUMO) of the isomers is ELUMO(β-Cl) > ELUMO(α-Cl) > ELUMO(ε-Cl) > ELUMO(γ-Cl) > ELUMO(δ-Cl). The energy gap between LUMO and HOMO was also sorted as Δ(L-H)(β-Cl) > Δ(L-H)(α-Cl) > Δ(L-H)(ε-Cl) > Δ(L-H)(γ-Cl) > Δ(L-H)(δ-Cl). In addition, the total dipole moment was classified as μ(ε-Cl) > μ(β-Cl) > μ(α-Cl) > μ(γ-Cl) > μ(δ-Cl). Finally, net charge of the ligand Azpy was also classified as QL(δ-Cl) > QL(γ-Cl) > QL(ε-Cl) > QL(α-Cl) > QL(β-Cl). All those parameters show that δ-Cl isomer displays the highest activity as antitumor drug when intercalating between the DNA basepairs Cytosine-Guanine/Cytosine-Guanine (CG/CG).
基金supported by the National Natural Science Foundation of China (20873017)the Natural Science Foundation of Jilin Province (20101154)
文摘The dynamic first hyperpolarizabilities of a series of 1,10-phenanthroline Ru（II） complexes were carried out using density functional theory （DFT）. The results indicate that these complexes have large second-order nonlinear optical （NLO） responses. Specially, complex 6b has a maximal first hyperpolarizability βtot value. The first hyperpolarizabilities can be tuned by changing the ancillary ligand, introducing electron-acceptor group NO2 and/or increasing r-conjugation on phenanthroline. Calculations on absorption spectra demonstrate that the second-order NLO responses of complexes in series a are ascribed to the intraligand charge transfer （ILCT）, while the complexes in series b exhibit metal-to-ligand charge transfer （MLCT） and lig- and-to-ligand charge transfer （LLCT） transition at relatively low-energy absorptions.
文摘In view of the growing interest for the synthesis of metal complexes and their interaction with DNA, we have synthesized and characterized two complexes containing ruthenium as metal center. The complexes are of the type [Ru（dppz）L4]（C104）2 where L are biologically important ligands such as pyrazole and dimethylpyrazole. The characterization of these complexes is done by 1 H NMR, 13C NMR, elemental analysis and mass spectroscopy. The interaction of these complexes with CT DNA was monitored and binding constants were determined using absorption and fluorescence spectroscopy. The mode of binding was found to be intercalative for both complexes and was determined using hydrodynamic viscosity studies. The complexes were further studied for photocleavage studies with supercoiled plasmid pBR322 DNA.
基金tlie National Natural Science Foundation of China(No.21675018)the Foundamental Research Funds for the Central Universities of China(No.DUTl 8LK37)the Foundation of the State Key Laboratory of Analytical Chemistry for Life Science,China(No.SKLACLS1705).
文摘A biomolecule-free photoelectrochemical(PEC) probe(denoted as Ru-1) was designed, synthesized and coupled with TiO2 nanoparticles(NPs) for the highly sensitive and selective PEC detection of Hg^2+, a model analyte with hypertoxicity to both human health and ecosystem. The probe Ru-1 was designed with Ru(Ⅱ) bipyridyl complex as the chromophore, thiocyanate ligand as the recognition unit, and carboxylate group as the linkage site to connect Ru-1 to TiO2 nanoparticles. Under irradiation, Ru-1 shows strong affinity to TiO2 and good photophysical properties of strong visible light absorption, slow electron-hole(e-h^+) recombination, and fast photoelectron injection to TiO2 nanoparticles via the bridge of 4-(2,2-bipyridin)-4-yl-thiophene moiety. However, the specific coordination of Hg^2+ with Ru-1 via the thiol moiety in the thiocyanate enlarges the band gap of tlie complex and reduces the photocurrent significantly. The synergistic interaction between TiO2 nanoparticles and the Ru-1 complex led to a selective PEC sensing strategy for Hg^2+ detection. Detectable linear ranges from 10^-12 g/mL to 10^-7 g/mL and from 10^-7g/mL to 10^-3 g/mL were obtained without the interference from possibly co-existed metal ions. The good analytical performances indicate the chemical probe based biomolecule-free PEC platform may offer a new route for the detection of biologically and environmentally important small molecules.
文摘Ground state geometries, natural bond orbital (NBO), analysis of frontier molecular orbitals (FMOs), analysis and spectral (RMN and UV-Visible) properties of five azopyridine ruthenium (II) complexes α-Cl, β-Cl, γ-Cl, δ-Cl and ε-Cl of RuCl2(Dazpy)2 have been theoretically studied by the Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) methods using two basis sets: Lanl2DZ and a generic basis set in gas or in chloroform solvent. Dazpy stands for 4,6-dimethyl-phenylazopyridine. Optimized geometry shows that, except β-Cl, all the other four isomers α-Cl, γ-Cl, δ-Cl and ε-Cl are C2 symmetrical. Otherwise, a good agreement was found between experimental and the calculated geometry and NMR data. Moreover, Lanl2DZ effective core potential basis set provides good chemical shifts and geometric properties. Furthermore, the prediction of the frontier orbitals (Highest Occupied Molecular Orbital or HOMO and Lowest Unoc-cupied Molecular Orbital or LUMO) shows that the most active isomer suita-ble for electronic reactions is admitted to be δ-Cl. Besides, the NBO analysis indicates that the Ru-N is formed by the electron delocalization of lone pair atomic orbital of N2 and Npy to Ru. Also, the strongest interactions between LP(N) with LP*(Ru) and LP(Cl) with LP*(Ru) stabilize the molecular struc-ture. In addition, NBO shows that the five d orbitals of Ru in the complex are organized so that there is no order of priority from one complex to another. Therefore, the transition LP(Ru) → π*(N1 = N2) corresponding to Metal to Li-gand Charge Transfer (MLCT) is in reality no more than d → π*. Besides, TDDFT prediction in chloroform solvent reveals that all the five isomerics complexes absorb in the visible region as well as efficient photosensitizers. What’s more, δ-RuCl2(dazpy)2 can potentially act as the excellent sensitizer with a large band of absorption in visible region and a small excited energy. This study can help design and find out the ability or properties of the com-plex to behave as sensitizer or potential cancer drugs.
